Cuprous cyanide-alkyl thioether or dithioether addition products as insectides



United States Patent 3,257,269 CUPROUS CYANIDE-ALKYL THIOETHER ORDITHIOETHER ADDITION PRODUCTS AS INSECTIDES Paul F. Warner, Phillips,and Bradford L. Archer and Richard D. Franz, Burger, Tex., assignors toPhillips Petroleum Company, a corporation of Delaware No Drawing.Original application Aug. '14, 1959, Ser. No. 833,697, now Patent No.3,064,025, dated Nov. 13, 1962. Divided and this application Mar. 2,1962, Ser.

I 4 Claims. (Cl. 167--22) This invention relates to the control orkilling of insects. In one of its aspects, it relates to a method inwhich addition compounds of a heavy metal cyanide and an alkyl thioetheror an alkyl dithioether are used for destroying insects such asgrasshoppers and cockroaches.

This application is a divisional of Serial Number 833,697, filed by usAugust 14, 1959, now Patent No. 3,064,025, issued November 13, 1962.

The cuprous cyanide addition compounds of di-n-butyl sulfide and2,5-dithiahexane have been prepared by adding the cyanide to thethioether. The additions have been made at room temperature. The cuprousn-butyl sulfonium cyanide is a viscous oil with a greenish tint and the2,5-dithiahexane-cuprous cyanide product is a white powder. It is anobject of the invention to provide an insecticide for killing insectssuch as grasshoppers and cockroaches. It is a further object of thisinvention to provide a method for killing insects such as grasshoppersand cockroaches.

Other aspects, objects and the several advantages of the invention areapparent from the present disclosure and the appended claims.

The alkyl thioethers and the alkyl dithioethers, as exemplified bydi-n-butyl sulfide and 2,5-dithiahexane, respectively, which areincluded within the scope of the present invention, are those whichcontain 1 to 12 carbon atoms in the alkyl group. The alkyl group can bea primary, secondary, or tertiary alkyl group. The dithioethers whichcontain sulfur attached to terminal carbon atoms, as in2,5-dithiahexane, are now preferred.

The preparation of the compounds used in this invention is set forth inmore detail and claimed in said Patent No. 3,064,025, which issuedNovember 13,1962.

According to the present invention, there is provided a method ofkilling insects which comprises applying to the insect an additionproduct of the invention.

EXAMPLE I Insecticide tests.The following tabulations show theinsecticidal properties of 2,5-dithiahexane-cuprous cyanide and cuprousdi-n-butyl sulfonium cyanide:

1 Average of two separate tests of grasshoppers each.

2 The meaning of 0.2 and 1.0 in the column labeled concentrationapplied, wt. percent means the insecticide was emulsified in water tothe specified concentration. A 0.2 weight percent application wouldcorrespond to 0.2 gram of insecticide being emulsified in 99.8 grams ofwater and emulsifier. Tritons X-151 and X-171 were used for2,5-dithiaheXane-CuCN addition product and Triton X-171 was used forcuprous n-butyl sulfonium cyanide. Water was used as the carrier in allof our tests. Other emulsifiers can be used, if desired, in lieu ofthose here mentioned.

3 The term powder means the insecticide, without carrier, was sprinkledinto the container containing the insects. The insects food, as well asthey themselves, came into contact with the powder. Approximately 1.0gram of insecticide, in powder form, was used in the tests.

Norm-The mortality rate for the cockroach control was nil.

3,257,269 Patented June 21, 1966 Table 2 Concentration Percent DeadCompound Applied, Wt. Grasshoppers, Percent 2 Days Cuprous di-n-butylsulfonium cyanide- 2 l. 0 Control Insects 50 1 See footnote 1, Table 1.1 See footnote 2, Table 1.

In the insecticide tests, the grasshoppers and cockroaches were placedin the same type containers but the control-insects were without theinsecticide. The containers used in the insect tests were cardboardquart boxes with one side cut away and covered with screen wire. Tengrasshoppers were placed in each container. Grass and a small treebranch were added to provide food and perching space for thegrasshoppers. Fresh grass was added each day during the test. Largebeakers (1000 cc.) were used in the cockroach tests. A thin layer ofVaseline was applied near the top of the beaker to prevent the roachesfrom escaping. Ten cockroaches were placed' in each beaker. A smallportion of cat food was also placed in each beaker as food for theroaches. The compounds to be tested were applied as emulsions in water,sprayed directly into the container wetting the insects and containerwalls as well as the grass and cat food. One container of insects wasleft unsprayed as a control for each run.

The following tabulation gives the results of a series of tests on theinsecticidal properties of 2,5-dithiahexanecuprous cyanide additioncompound and cuprous n-butyl sulfonium cyanide. These tests were run todetermine whether the control mortality rate for grasshoppers could belowered while still obtaining the high mortality rate for theinsecticide.

As is seen, the control mortality rates for grasshoppers aresubstantially lower than those in the earlier tables of this example.The high mortality rate of the treated insecticides was about the sameas before. The mortality rate for. the cockroach control was nil. Aconcentration of 1.0 weight percent is now preferred for satisfactorykill power under most ordinary conditions.

The heavy metals, the cyanides of which are to be included whenconsidering this disclosure are: copper, zinc,- silver, gold, mercury,lead, cadmium, nickel, cobalt, palladium, platinum and barium.

The compounds now preferred to be used in method of the inventioninclude the 2,5-dithiahexane-cuprous cyanide addition product andcuprous-di-n-butyl sulfonium cyanide.

Reasonable variation and modification are possible within the scope ofthe foregoing disclosure and the appended claims to the invention, theessence of which is that there have been provided a composition and amethod for control or killing of insects such as grasshoppers androaches, the composition comprising an effective amount upon applicationof a heavy metal cyanide addition prod- Q net of an alkyl thioether and/or an alkyl dithioether, as

described.

We claim:

1. A method of killing an insect which comprises applying thereto anaddition product of cuprous cyanide and a compound selected from thegroup consisting of alkyl thioethers. and alkyl dithioethers in whichany alkyl group contains 1-12 carbon atoms.

2. A method for killing a cockroach which comprises applying thereto anaddition product of cuprous cyanide and a compound selected from thegroup consisting of alkyl thioethers and alkyl dithioethers in which anyalkyl group contains 1-12 carbon atoms.

3. A method for killing an insect which comprises applying aninsecticidal amount of 2,5-dithiahexane-cuprous cyanide addition productto said insect.

4. A method of killing an insect which comprises applying an effectiveamount of cuprous-n-butyl sulfonium cyanide to said insect.

References Cited by the Examiner UNITED STATES PATENTS 8/1961 Scott eta1. 167-22 1/1962 Franz et a1. 167-22 OTHER REFERENCES Frear, D.E.H.:3rd edition, New York, Van Nostrand Co., 1955, SB951F7, note especiallypage 280.

JULIAN S. LEVITT, Primary Examiner.

FRANK CACCIAPAGLIA, JR., Examiner.

1. A METHOD OF KILLING AN INSECT WHICH COMPRISES APPLYING THERETO ANADDITION PRODUCT OF CUPROUS CYANIDE AND A COMPOUND SELECTED FROM THEGROUP CONSISTING OF ALKYL THIOETHERS AND ALKYL DITHIOETHERS IN WHICH ANYALKYL GROUP CONTAINS 1-12 CARBON ATOMS.